N-benzyltriazole compounds and plant growth regulant compositions

ABSTRACT

N-BENZYLTRIAZOLES OF THE FORMULA   (TRIAZOLYL-C(-A)(-B)-),(X)M-BENZENE   IN WHICH TRIAZOYLY IS 1,2,4 OR 1,2,3 TRIAZOLYL WHICH MAY BE SUBSTITUTED; X IS HALOGN, TRIFLUOROMETHYL, LOWER ALKYL, LOWER ALKOXY, LOWER ALKLTHIO, ARYL, NITRO, CYCANO OR (ALKYLATED) AMINO; M IS 0, 1 OR 2; A IS OPTIONALLY SUBSTITUTED PHENYL, PYRIDYL, ALKYL OR CYCLOALKYL; AND B IS A 5-MEMBERED HETEROCYCLIC RING, E.G., N-HETEROCYCLE; AND HEIR SALT ARE OUTSTANDINGLY EFFECTIVE IN REGULATING PLANT GROWTH, E.G., INHIBITING, STIMULATING OR ALTERING PLANT GROWTH.

United States Patent 3,801,590 N-BENZYLTRIAZOLE COMPOUNDS AND PLANTGROWTH REGULANT COMPOSITIONS Wilfried Draber, Wuppertal-Elberfeld, ErikRegel, Wuppertal-Cronenberg, Karl-Heinz Buchel, Wnppertal- Elberfeld,Ludwig Ene, Cologne, and Robert R. Schmidt, Leverkusen-Rheindorf,Germany, assignors to Bayer Aktiengesellschaft, Leverkusen, Germany NoDrawing. Filed Dec. 9, 1970, Ser. No. 96,574 Claims priority,application Germany, Dec. 24, 1969, P 19 64 995.7 Int. Cl. C0711 85/22US. Cl. 260-307 H 9 Claims ABSTRACT OF THE DISCLOSURE N-Benzyltriazolesof the formula A- l trlazolyl B in which triazolyl is 1,2,4 or 1,2,3triazolyl which may be substituted;

X is halogen, trifluoromethyl, lower alkyl, lower alkoxy, loweralkylthio, aryl, nitro, cyano or (alkylated) amino;

m is 0, 1 or 2;

A is optionally substituted phenyl, pyridyl, alkyl or cycloalkyl; and

B is a S-membered heterocyclic ring, e.g., N-heterocycle;

and their salts are outstandingly eifective in regulating plant growth,e.g., inhibiting, stimulating or altering plant growth.

The present invention relates to certain new N-benzyltriazole compounds,to compositions containing them and to their use as agents for theregulation of plant growth.

It is known that succinic acid 2,2-dimethylhydrazide,2-chloroethyltrimethylammonium chloride and maleic acid hydrazide can beused for regulating the growth of higher plants (see Cathey, H. M.,Physiology of Growth- Retarding Chemicals, Ann. Rev. Plant Phys. 15,pages 271-302 (1964), German published specification 1,238, 052 and US.Pat. Nos. 2,575,954; 2,614,912; 2,614,916; 2,614,917 and 2,805,926). Theactivity of the said compounds of the prior art at low concentrations ofactive compound, is however, in many cases unsatisfactory and, at highconcentrations, in some cases, plant damage occurs.

Surprisingly, the novel N-benzyltriazole compounds of this inventionshow generally stronger plant-growthinfiuencing activity than thecompounds of the prior art. The compounds according to the inventiontherefore represent an enrichment of the art.

The compounds of the invention are N-benzyltriazoles of the formula IA'C-trlazolyl in which triazolyl is j N N=N N l or N wherein E is oxygenor sulfur or a radical of the formula alkyl or -N- aryl and Y ishydrogen, lower alkyl, halogen or an optionally substituted arylradical, and n is 0, 1 or 2, and their salts.

The compounds of the invention exhibit strong plantgrowth-regulatingproperties.

Of the salts of the substituted N-benzyltriazoles of the Formula (I),those of acids tolerated by plants are, of course, preferred for thetreatment of plants. Examples of such acids are the halogen hydracids,phosphoric acids, sulfonic acids, aliphatic monoand di-carboxylic acidsas well as hydroxycar-boxylic acids.

The present invention also provides a process for the production of thecompounds according to the present invention, in which a benzyl halideof the formula A-(J-Hal in which X, m, A and B have the meanings statedabove, and

Hal stands for a chlorine or bromine atom is reacted with a triazole ofthe formula in which R and R have the meanings stated above in thepresence of a diluent, preferably a polar organic solvent, and anacid-binding agent, and, if required, the resulting N-benzyltriazole isconverted into a salt thereof.

3 If phenyl 4 fiuorophenyl (5-methylisoxazol-3-yl)- chloromethane and1,2,4-triazole are used as starting materials, the reaction course canbe represented by the following equation:

N J) (IV) 2-thienyl "CH: N

\O/ 5-(3-methyl)-isoxazolyl \N/ 3-(5-methyD-isoxazolyl o1 -o1 1 N s5-(3,4-dichloro)-isothiazolyl -N l LCHa S 5-(2, 4-dimethyl)-thiazolylPIT C H: s 2-(4-methyl) -thiazolyl 2-(1-methyl) -lmidaz0lyl5-(2,3-dlmethyl) -pyraz0lyl As examples of the benzyl halides which canbe used in the preparative process according to the invention, there maybe mentioned:

bis-phenyl- (thien-2-yl -chloromethane bis-phenyl-3-methyl-isoxazol-5-yl -chloromethane phenyl-4-fluorophenyl- (5-methyl-isoxazol-3-yl) chloromethane phenyl-4-chlorophenyl-(l-methyl-imidazol-Z-yl) chloromethane phenyl-diphenylyl-(l-methyl-imidazol-Z-yl -chloromethane phenyl-4-methylmercaptophenyl-3-methyl-isoxazol- S-yl -chloromethane phenyl-4-methylmercaptophenyl-(S-methyl-isoxazol- 3-yl chloromethane phenyl-4-chlorophenyl-(5-methyl-is0xazo1-3-yl)- chloromethane phenyl-4-fluorophenyl-S-methyl-isoxazol-S-yl) chloromethane phenyl-4-tert.-b utylphenyl-1-methyl-imidazol-2-yl)- chloromethane phenyl-3 -methylphenyl-(l-methyl-imidazol-Z-yl) chloromethane phenyl-3-trifiuoromethyl-(1-methyl-imidazol-2-yl)- chloromethane phenyl-4-nitrophenyl-(thien-Z-yl) -chloromethane (pyrid-4-yl) -phenyl-3-methyl-isoxazol-5-yl)- chloromethanephenyl-4-methoxyphenyl-(S-methylisoxazol-3-yl)- chloromethane The benzylhalides of the Formula H are new but can be prepared by reacting acarbinol of the general formula A, B, X and m have the meanings statedabove with an agent for halogenating tertiary alcohols. Especiallysuitable halogenating agents are acid chlorides, such as thionylchloride, thionyl bromide, phosphoryl bromide, phosphoryl chloride,phosphorus trichloride, phosphorus tribromide, acetyl chloride andacetyl bromide. The reaction can be carried out either in the absence orpresence of a solvent; suitable solvents include ethers, methylenechloride, benzene and toluene. The reaction is carried out attemperatures of 0 to 150 C., preferably at 20 to C. If the five-memberedheterocyclic substituent of the carbinol (V) contains nitrogen, thehalides (II) are frequently obtained in the form of their halogenhydracid salts.

The triazoles to be used as starting materials are defined by theFormulae IIIa and IIIb. In these formulae, R and R stand preferably forhydrogen, methyl or ethyl. The 1,2,4-triazolyl derivatives (IIIa) arepreferred. As an example, there may be mentioned 1,2,4-triazole, whichis known.

As diluents for the reaction of the halide (II) with the triazole (Illa)or (IIIb), especially suitable are polar organic solvents, the preferredsolvents being nitriles (such as acetonitrile), nitromethane, dimethylformamide, hexamethyl-phosphoric acid triamide, acetone and chloroform.

As the acid-binding agent, an excess of the triazole (IIIa) or (IHb) issuitable. Organic bases of low nucleophilicity, such as triethylamine,lutidine, quinoline, or inorganic bases, such as potassium carbonate,magnesium oxide or calcium carbonate, can also be used.

The reaction temperatures can be varied within a fairly wide range. Ingeneral, the work is carried out at from 0 to 150 C. preferably from 20to 100 C.

When carrying out the process according to the invention, the triazoleis expediently used in at least the equivalent amount. If one wishes todispense with an auxiliary agent for acid-binding purposes, the triazoleshould be used in at least twice the molar (equivalent) amount, and inthree times the molar (equivalent) amount if a hydrohalide of theFormula II is used. If an auxiliary agent is employed for acid-binding,this should be used in at least the equivalent amount, preferably inexcess.

A preferred embodiment of the process comprises adding dropwise asolution of the halide (II) to a solution of the triazole (IIIa) or(IIIb), which also contains the acid-binding agent for exampletriethylamine, in a polar organic solvent, such as acetonitrile, at anelevated temperature, preferably at 70 to 80 C.

It may furthermore be expedient to carry out, in one of theabove-mentioned polar solvents, the preliminary halogenation of theappropriate carbinol (V) and to follow directly, without intermediateisolation of the resulting halide, with the reaction according to theinvention using a suitable triazole.

Working up is effected in any customary manner, for example byconcentration, washing with water, and recrystallization. The compoundscan also be made to separate by addition of water.

The active compounds according to the invention interfere with thephysiological phenomena of plant growth and can therefore be used asplant-growth regulators.

The different effects of an active compound depend essentially on thepoint in time of the application, with reference to the developmentstage of the seed or the plant, as well as on the concentration applied.

Plant-growth regulators are used for various purposes which areconnected with the development stage of the plant.

Thus, with plant-growth regulators the seed dormancy can be broken inorder to cause the seeds to germinate at a certain desired time at whichthe seed itself shows no readiness to germinate. The seed germinationitself can either be inhibited or promoted by such active compounds,depending on the concentration applied. This inhibition or promotionrelates to the seedling development.

The bud dormancy of the plants, that is to say the endogenic annualcycle, can be influenced by the active compounds, so that the plants,for example, shoot or blossom at a point in time at which they normallyshow no readiness to shoot or bloom.

The shoot or root growth can be promoted or inhibited by the activecompounds in manner dependent on the concentration. Thus, it is possibleto inhibit very strongly the growth of the fully formed plant, or tobring the plant as a whole to a more robust habitus or to produce adwarf growth.

A use of the active compounds which is of economic interest is thesuppression of grass growth at roadsides and waysides. Further, thegrowth of lawns can be inhibited by growth regulators, so that thefrequency of grass-cutting (of lawn-mowing) can be reduced.

During the growth of the plant, the branching to the side can bemultiplied by a chemical breaking of the apical dominance. This can beutilized in, for example, the case of propagation of plants by cuttings.In a manner dependent on the concentration of the compounds it is alsopossible to inhibit the growth of side-shoots, for example in order toprevent, in tabacco plants, the formation of side-shoots afterdecapitation and thus to promote the leaf growth.

In the case of the influencing of blossom formation, there can beachieved, in a manner dependent on the concentration and the point intime of the application, either a retarding or an acceleration of bloomformation. Under certain circumstances, a multiplication of blossominitiation can also be obtained, these eflfects occurring when theappropriate treatments are carried out at the time of the normal blossomformation.

The influence of the active compounds on the foliage of the plants canbe so regulated that a defoliation is achieved, for example in order tofacilitate harvesting or to reduce transpiration at a time at which theplants are to be transplanted.

Fruit initiation can be promoted so that more, or seedless, fruits areformed (parthenocarpy). Under certain conditions, the premature fall offruit can also be prevented, or the fruit fall can be promoted to acertain extent in the sense of a chemical thinning out. The promotion ofthe fruit fall can, however, also be so exploited that the treatment iseffected at the time of the harvest, thereby facilitating theharvesting.

The active compounds according to the present invention can be convertedinto the usual formulations, such as solutions, emulsions, suspensions,powders, pastes and granulates. These may be produced in known manner,for example by mixing the active compounds with extenders, that is,liquid or solid diluents or carriers, optionally with the use ofsurface-active agents, that is, emulsifying agents and/or dispersingagents. In the case of the use of water as an extender, organic solventscan, for example, also be used as auxiliary solvents.

As liquid diluents or carriers, there are preferably used aromatichydrocarbons, such as xylenes or benzene, chlorinated aromatichydrocarbons, such chlorobenzenes, paraffins, such as mineral oilfractions, alcohols, such as methanol or butanol, or strongly polarsolvents, such as dimethyl formamide or dimethyl sulfoxide, as well aswater.

As solid diluents or carriers, there are preferably used ground naturalmineral, such as kaolins, clays, talc or chalk, or ground syntheticminerals, such as highlydispersed silicic acid or silicates.

Preferred examples of emulsifying agents include nonionic and anionicemulsifiers, such as polyoxyethylenefatty acid esters,polyoxyethylene-fatty alcohol ethers, for example alkylarylpolyglycolethers, alkylsulfonates and aryl sulfonates; and preferred examples ofdispersing agents include lignin, sulfite waste liquors and methylcellulose.

The formulations contain, in general, between 0.1 and 95, preferablybetween 0.5 and 90, percent by weight of active compound.

The active compounds may be applied as such or n the form of theirformulations or of the application forms prepared therefrom, such asready-to-use solutions, emulsifiable concentrates, emulsions,suspensions, spray powders, pastes, soluble powders, dusting agents andgranulates. Application takes place in any customary manner, for exampleby watering, squirting, spraying, scattering or dusting.

The concentrations of active compound for actual application can bevaried within a fairly wide range. In general, concentrations of 0.005to 2%, preferably from 0.01 to 0.5% are used.

Furthermore, there are applied, in general, 0.1 to kg., preferably 1 to10 kg, of active compound per hectare of soil area.

For the application time, it is usually valid to say that application ismost favorable when a strong elongation growth has occurred, that is atthe so-called time of greatest shooting. In ligneous plants, applicationis preferred shortly before commencement of shooting. Thus,

in contrast to the application of insecticides and fungicides, theapplication of the growth regulators is preferably effected in a givenspace of time, the precise delimitation of which is governed by theclimatic and vegetative cirvention alone or in the form of a compositioncontaining as active ingredient a compound of the present invention inadmixture with a solid or liquid diluent or carrier.

Some of the compounds to be used according to the cumstances- 5invention are also effective against plant-damaging fungi i present{n.ventwn 9 provide? a p g z (for example against mildew species) andbacteria. An u 3 mg composltlon cqntalmpg acme. mgre i a activityagainst mold fungi and yeasts has also been pound of the presentinvention in admixture with a solid noted diluent or carrier or inadmixture with a liquid diluent or f th d t th carrier containing asurface-active agent. 10 e ac y o e compoun S mg 0 f The presentinvention also provides a method of concan f seen from the examples 111which trolling the growth of plants which comprises applyin to thefollowlng test compounds lllustratlvc of the invention the plants orseeds thereof a compound of the present inwere employed:

TABLE Compound number Chemical name Structure 1(4-fluoro-phenyl)-phenyl-(5-methyl-isoxazo1-3-y1)-(1,2,4-triazol-1-yl)-methaneN Ha 2(4-ehloro-phenyl)-phenyl-(5-methyl-isoxazol-3-yl)-(1,2,4-trlazol-1-yl)methane-N: I \=N N CH:-

3(ii-methyl-phenyl)-phenyl-(1-methyl-imldazol-2-yl)-(1,2,4-trlazol-1-yl)-methaneCH KN: l

N N-CH| 4Bis-phenyl-(5-methyl-lsoxazol-3-yl)-(1,2,4-trlazol-1-y1)-methane KN: Q=,l

I N CH3---(L 5(efluormphenyl)-phenyl-(3-methy1-isoxazol-5-y1)-(1,2,4-trlazol-1-yl)methane.

CHa-QL 6(4-ehloro-pheny1)-phenyl-(l-methyl-imldazol-Z-yl)-(1,2,4-trlazol-1-yl)-methane..Cl

TABLE Coutinued Compound number Chemical name Structure 7(4-terL-butylphenyl)-phenyl-(1-methyl-imidazol-2-yl)-(1,2,4-triazol-1-yl)-CH;

methane.

GHa- C I A N N-CH:

8(iphenyl-phenyl)-phenyl-(l-methyl-imldazol-Z-yl)-(1,2,4-triazol-l-yl)-methane.

I(N: Q2 i N-CH:

EXAMPLE A stated amount of solvent which contained the stated Growthinhibition/linseed test Solvent: 40 parts by weight acetone Emulsifier:0.25 part by weight alkylaryl polyglycol ether To produce a suitablepreparation of active compound, 1 part by weight of active compound wasmixed with the stated amount of solvent which contained the statedamount of emulsifier, and the concentrate was diluted with a disodiumhydrogen phosphate-potassium dihydrogen phosphate buffer solution (pH 6)to the desired concentration.

Batches of 25 linseeds were laid out on two filter papers in a Petridish. 10 ml. of the preparation of active compound were pipetted intoeach dish. Germination of the seeds took place in the dark at C.

After 3 days, the length of the roots was determined and the growthinhibition compared with the control plant was expressed as apercentage. 100% denoted the standstill of growth, and 0% denoted agrowth corresponding to that of the untreated plant.

The active compounds, the concentrations of the active compounds inp.p.m. =mg./kg.) and results can be seen from the following table.

EXAMPLE B Growth inhibition/oat grains Sol-vent: 40 parts by weightacetone Emulsifier: 0.25 parts by weight alkylaryl polyglycol ether Toproduce a suitable preparation of active compound, 1 part by weight ofactive compound was mixed with the amount of emulsifier, and theconcentrate was diluted with a disodium hydrogen phosphate-potassiumdihydrogen phosphate buffer solution (pH 6) to the desiredconcenaration.

Batches of 25 oat grains were laid out on two filter papers in a Petridish. 10 m1. of the preparation of active compound were pipetted intoeach dish. Germination of the seeds took place in the dark at 25 C.

After 3 days, the length of the shoot was determined and the growthinhibition compared with the control plant was expressed as apercentage. denoted the standstill of growth, and 0 denoted a growthcorresponding to that of the untreated plant.

The active compounds, concentrations of the active compuonds in p.p.m.=mg./kg.) and the results can be seen from the following table.

TABLE B Growth inhibition/oat grains test Percent with- Active compound50 p.p.m. 250 p.p.m.

Water (control) 0 0 Succinio acid 2,2dimethy1hydrazide (known)..-(2-clgoroethyl)-trlmcthyl-ammonium chloride Growth inhibition/appleseedlings Solvent: 40 parts by weight acetone Emulsifier: 0.25 parts byweight alkylaryl polyglycol ether To produce a suitable preparation ofactive compound, 1 part by weight of active compound was mixed with thestated amount of solvent which contained the stated amount ofemulsifier, and the concentrate was diluted with a disodium hydrogenphosphate-potassium dihydro- TABLE C Growth inhibition/apple seedlingstest Percent inhibition Acti ve compound: with 500 p.p.m. Water(control) Succinic acid 2,2-dimethylhydrazide (known) 23 (2chloroethyl)-trimethyl-ammonium chloride 25 Compound 1 50 Compound 4 43Compound 5 57 EXAMPLE D Growth inhibition/tomato plants Solvent: 40parts by weight acetone Emulsifier: 0.25 parts by weight alkylarylpolyglycol ether To produce a suitable preparation of active compounds,1 part by weight of active compound was mixed with the stated amount ofsolvent which contained the stated amount of emulsifier, and theconcentrate was diluted with a disodium hydrogen phosphate-potassiumdihydrogen phosphate buffer solution (pH 6) to the desiredconcentration.

Tomato plants of a height of cm. were sprayed with a preparation whichcontained 500 p.p.m. of active compound.

After 8 days, the percentage inhibition of the treated plants comparedwith the untreated control plant was determined. With 100% inhibition,no growth was present; with 0% inhibition, the growth corresponded tothat of the control plant.

The active compounds, concentration of active compound in p.p.m.=mg./kg.) and the results can be seen from the following table.

TABLE D Growth inhibition/tomato plants test Percent inhibition withActive compound: 500 p.p.m.

Water (control) 0 Succinic acid-2,2-dimethylhydrazide (known)(2-chloroethyl)-trimethyl ammonium chloride Solvent: parts by weightacetone Emulsifier: 0.25 parts by weight alkylaryl polyglycol ether Toproduct a suitable preparation of active compound, 1 part by weight ofactive compound was mixed with the stated amount of solvent whichcontained the stated amount of emulsifier, and the concentrate wasdiluted with a disodium hydrogen phosphate-potassium dihydrogenphosphate buffer solution (pH 6) to the desired concentrations.

Beans (Phaseolus vulgaris) 10 cm. high were sprayed with preparationswhich contained 500 p.p.m. of active compound.

After 8 days, the length of the treated plants compared with theuntreated control plant was determined.

The active compounds, concentrations of active compound in p.p.m.(=mg./kg.) and the results can be seen from the following table.

Length in cm. with a concentration of active compound of Activecompounds: 500 p.p.m. Water (control) 26 Maleic acid hydrazide (known 12Compound 1 10.5 Compound 2 10.0 Compound 5 10.0 Compound 8 11.5

The following example illustrates the preparative process of the presentinvention.

Example 1.Preparation of bis-phenyl-(3-methylisoxa- 201-5 -yl)1,2,4-triazol-1-yl) -methane 5 4 1 0| 3 2 CH3" N Preliminary product: 21grams (0.08 mole) bis-phenyl- (3-methylisoxazol-5-yl)-carbinol wereboiled in 250 ml. methylene chloride with 10.1 grams (0.085 mole)thionyl chloride until the evolution of gas ceased. The solution wasconcentrated in a vacuum.

Reaction: The bis phenyl (3 methylisoxazol 5- yl) chloromethane obtainedabove was, without isolation, dissolved in 150 ml. acetonitrile, and thesolution was added dropwise to a boiling solution of 16.6 grams (0.24mole) 1,2,4 triazole in ml. acetonitrile. The mixture was boiled for 30minutes, concentrated, and ice water was added to the residue. 20.2grams bis phenyl- (3 methylisoxazol 5 yl) 1,2,4 triazol 1 yl)- methaneof the melting point 167-169 C. were obtained in the form of colorlesscrystals.

Yield: 79% of the theory (with reference to the carbinol used aspreliminary product).

Starting material: The carbinol required as a starting material wasobtained in the following manner:

From 31.4 grams (0.2 mole) bromobenzene and 4.86 grams (0.2 mole)magnesium turnings in ml. ether there was prepared a solution ofphenylmagnesium bromide which Was added dropwise at -5 C. to a solutionof 18.7 grams (0.1 mole) 5-benzoyl-3-methylisoxazole. Heating waseffected slowly, followed by boiling under reflux for one hour andpoured onto ice. After acidification with 25 ml. hydrochloric acid, theethereal phase was separated; washing with bicarbonate solution waseffected, followed by drying and concentration. The residue wascrystallized with ether/petroleum ether. 21 gramsbisphenyl-(3-methylisoxazol-5-yl)-carbinol of the melting point 116-118"C. were obtained.

13 Yield: 80% of the theory.

The following compounds were prepared in an analogous manner:

B M.P. C.)

S-methyl-isdiiazoH-yl. 99-100 1-methyl-imidazol-2-yl..-.. 142

3-methy1-isoxazol'5Fyl.... 94-97 5-methy1-isoxazol-3-y1. 116-117 01 .do104-106 8 4-F 3-methyl-isoxazol-5-yl- 127-128 9 C(CH3)31-methylim1dazol-2-y1.-... 130 10 3-CH3 ---do 120 It will be understoodthat the foregoing specification and examples are illustrative and notlimitative of the present invention in that many other embodiments ofthe invention will suggest themselves to those skilled in the art.

What is claimed is: 1. N-benzyltriazole compound of the formula 3.A(l3triazolyl in which triazolyl is N N i N I 14 wherein R and R arehydrogen; and

X is halogen, lower alkyl, lower alkylthio or phenyl; m is 0, 1 or 2; Ais phenyl; and B is isoxazolyl, isothiazolyl, methylisoxazolyl ormethylisothiazolyl.

2. Compound as claimed in claim 1 wherein B is isoxazol-3-yl.

3. Compound as claimed in claim 1 wherein B is methylisoxaz0l-3-yl.

4. Compound as claimed in claim 1 wherein B is methyl-isothiazolyl.

5. Compound as claimed in claim 1 wherein B is isothiazolyl.

6. Compound as claimed in claim 1 designated as (4-fluoro-phenyl)-phenyl-(S-methyl-isoxazol 3 yl)-(1,2,4-triazol-1-yl)-methane.

7. Compound as claimed in claim 1 designated as (4- chloro-phenyl)-phenyl-(S-methyl-isoxazol 3 yl) 1,2,4- triazo1-1-yl)-methane.

8. Compound as claimed in claim 1 designated as hisphenyl (5methyl-isoxazol 3 y1)-l,2,4-triazol-1-yl)- methane.

9. Compound as claimed in claim 1 designated as (4- fluoro-phenyD-phenyl(3-methyl-isoxazole S-yl) 1,2,4- triazol-1-y1)-methane.

References Cited UNITED STATES PATENTS 6/1964 Brown 260302 DONALD G.DAUS, Primary Examiner R. V. RUSH, Assistant Examiner U.S. Cl. X.R.

